Thiol ester compositions and processes for making and using same

Abstract

Thiol ester compositions, methods of making the thiol ester compositions, and methods of using the thiol ester compositions are provided. In some embodiments, the thiol ester compositions include thiol esters, hydroxy thiol esters and cross-linked thiol esters. The thiol ester composition can be used to produce cross-linked thiol esters, sulfonic acid-containing esters, sulfonate containing esters and thioacrylate containing esters. The thiol ester compositions can be used to produce polythiourethanes. The polythiourethanes can be used in fertilizers and fertilizer coatings.

1. A thiol ester composition comprising:
 thiol ester molecules prepared from an unsaturated triglyceride, 
 the thiol ester molecules having
 an average of at least 1.5 ester groups per thiol ester molecule, 
 an average of at least 1.5 thiol groups per thiol ester molecule, and 
 an average molar ratio of cyclic sulfides to thiol groups of between 0.05 and 1. 
 
 
     
     
       2. The thiol ester composition of  claim 1 , wherein the thiol ester molecules have a molar ratio of carbon-carbon double bonds to thiol groups of less than 1.5. 
     
     
       3. The thiol ester composition of  claim 1 , wherein the thiol ester molecules have an average of greater than 5 weight percent thiol sulfur. 
     
     
       4. The thiol ester composition of  claim 1 , wherein thiol ester molecules have an average ranging from 8 to 10 weight percent thiol sulfur. 
     
     
       5. The thiol ester composition of  claim 1 , wherein the thiol ester molecules have an average of less than 30 mole percent total sulfur present as cyclic sulfides. 
     
     
       6. The thiol ester composition of  claim 1 , wherein greater than 40 percent of thiol ester molecule total side chains contain sulfur. 
     
     
       7. The thiol ester composition of  claim 1 , wherein the unsaturated triglyceride is prepared from soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       8. The thiol ester composition of  claim 1 , wherein the unsaturated triglyceride is prepared from soybean oil. 
     
     
       9. The thiol ester composition of  claim 1 , wherein the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, and 
 an average of 2 to 4 thiol groups per thiol ester molecule. 
 
     
     
       10. The thiol ester composition of  claim 7 , wherein the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       11. The thiol ester composition of  claim 8 , wherein the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       12. The thiol ester composition of  claim 1 , wherein the thiol ester molecules have
 an average of from 1.5 to 8 ester groups per thiol ester molecule, 
 an average of from 1.5 to 9 thiol groups per thiol ester molecule, and 
 an average of at least 5 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       13. The thiol ester composition of  claim 1 , wherein the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       14. A thiol ester composition comprising:
 thiol ester molecules prepared from an unsaturated natural source oil, 
 the thiol ester molecules having
 an average of at least 1.5 ester groups per thiol ester molecule, 
 an average of at least 1.5 thiol groups per thiol ester molecule, and 
 an average molar ratio of cyclic sulfides to thiol groups of between 0.05 and 1. 
 
 
     
     
       15. The thiol ester composition of  claim 14 , wherein the thiol ester molecules have a molar ratio of carbon-carbon double bonds to thiol groups of less than 1.5. 
     
     
       16. The thiol ester composition of  claim 14 , wherein the thiol ester molecules have an average of greater than 5 weight percent thiol sulfur. 
     
     
       17. The thiol ester composition of  claim 14 , wherein thiol ester molecules have an average ranging from 8 to 10 weight percent thiol sulfur. 
     
     
       18. The thiol ester composition of  claim 14 , wherein the thiol ester molecules have an average of less than 30 mole percent total sulfur present as cyclic sulfides. 
     
     
       19. The thiol ester composition of  claim 14 , wherein greater than 40 percent of thiol ester molecule total side chains contain sulfur. 
     
     
       20. The thiol ester composition of  claim 14 , wherein the thiol ester molecules have
 an average of from 1.5 to 8 ester groups per thiol ester molecule, 
 an average of from 1.5 to 9 thiol groups per thiol ester molecule, and 
 an average of at least 5 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       21. The thiol ester composition of  claim 20 , wherein the unsaturated natural source oil is soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       22. The thiol ester composition of  claim 20 , wherein the unsaturated natural source oil is soybean oil. 
     
     
       23. The thiol ester composition of  claim 14 , wherein the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       24. The thiol ester composition of  claim 23 , wherein the unsaturated natural source oil is soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       25. The thiol ester composition of  claim 23 , wherein the unsaturated natural source oil is soybean oil. 
     
     
       26. A thiol ester composition comprising:
 thiol ester molecules prepared from an unsaturated triglyceride, 
 the thiol ester molecules having
 an average of at least 1.5 ester groups per thiol ester molecule, 
 an average of at least 1.5 thiol groups per thiol ester molecule, and 
 a secondary thiol group. 
 
 
     
     
       27. The thiol ester composition of  claim 26 , wherein the thiol ester molecules have a molar ratio of carbon-carbon double bonds to thiol groups of less than 1.5. 
     
     
       28. The thiol ester composition of  claim 26 , wherein the thiol ester molecules have an average of greater than 5 weight percent thiol sulfur. 
     
     
       29. The thiol ester composition of  claim 26 , wherein thiol ester molecules have an average ranging from 8 to 10 weight percent thiol sulfur. 
     
     
       30. The thiol ester composition of  claim 26 , wherein the thiol ester molecules have an average of less than 30 mole percent total sulfur present as cyclic sulfides. 
     
     
       31. The thiol ester composition of  claim 26 , wherein greater than 40 percent of thiol ester molecule total side chains contain sulfur. 
     
     
       32. The thiol ester composition of  claim 26 , wherein the thiol ester molecules have
 an average of from 1.5 to 8 ester groups per thiol ester molecule, 
 an average of from 1.5 to 9 thiol groups per thiol ester molecule, and 
 an average of at least 5 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       33. The thiol ester composition of  claim 32 , wherein the unsaturated triglyceride is prepared from soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       34. The thiol ester composition of  claim 32 , wherein the unsaturated triglyceride is prepared from soybean oil. 
     
     
       35. The thiol ester composition of  claim 26 , wherein the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       36. The thiol ester composition of  claim 35 , wherein the unsaturated triglyceride is prepared from soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       37. The thiol ester composition of  claim 35 , wherein the unsaturated triglyceride is prepared from soybean oil. 
     
     
       38. A thiol ester composition comprising:
 thiol ester molecules prepared from an unsaturated natural source oil, 
 the thiol ester molecules having
 an average of at least 1.5 ester groups per thiol ester molecule, 
 an average of at least 1.5 thiol groups per thiol ester molecule, and 
 a secondary thiol group. 
 
 
     
     
       39. The thiol ester composition of  claim 38 , wherein the thiol ester molecules have a molar ratio of carbon-carbon double bonds to thiol groups of less than 1.5. 
     
     
       40. The thiol ester composition of  claim 38 , wherein the thiol ester molecules have an average of greater than 5 weight percent thiol sulfur. 
     
     
       41. The thiol ester composition of  claim 38 , wherein thiol ester molecules have an average ranging from 8 to 10 weight percent thiol sulfur. 
     
     
       42. The thiol ester composition of  claim 38 , wherein the thiol ester molecules have an average of less than 30 mole percent total sulfur present as cyclic sulfides. 
     
     
       43. The thiol ester composition of  claim 38 , wherein greater than 40 percent of thiol ester molecule total side chains contain sulfur. 
     
     
       44. The thiol ester composition of  claim 38 , wherein the thiol ester molecules have
 an average of from 1.5 to 8 ester groups per thiol ester molecule, 
 an average of from 1.5 to 9 thiol groups per thiol ester molecule, and 
 an average of at least 5 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       45. The thiol ester composition of  claim 44 , wherein the unsaturated natural source oil is soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       46. The thiol ester composition of  claim 44 , wherein the unsaturated natural source oil is soybean oil. 
     
     
       47. The thiol ester composition of  claim 38 , wherein the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
     
     
       48. The thiol ester composition of  claim 47 , wherein the unsaturated natural source oil is soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       49. The thiol ester composition of  claim 47 , wherein the unsaturated natural source oil is soybean oil. 
     
     
       50. A process for producing a thiol ester composition comprising the steps of:
 a) contacting hydrogen sulfide and an unsaturated ester composition comprising unsaturated triglycerides, 
 the unsaturated triglycerides having
 an average of at least 1.5 ester groups per unsaturated triglyceride molecule, and 
 an average of at least 1.5 carbon-carbon double bonds per unsaturated triglyceride molecule; and 
 
 b) reacting the hydrogen sulfide and the unsaturated triglycerides to form a thiol ester composition comprising thiol ester molecules, 
 the thiol ester molecules having
 an average of at least 1.5 ester groups per thiol ester molecule, 
 an average of at least 1.5 thiol groups per thiol ester molecule, and 
 an average molar ratio of cyclic sulfides to thiol groups of between 0.05 and 1. 
 
 
     
     
       51. The process of  claim 50 , wherein the unsaturated triglycerides are prepared from soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       52. The process of  claim 50 , wherein the unsaturated triglycerides are prepared from soybean oil. 
     
     
       53. The process of  claim 50 , wherein the unsaturated triglycerides are prepared from soybean oil, corn oil, castor bean oil, or canola oil, and
 the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
 
     
     
       54. The process of  claim 50 , wherein the step of reacting the hydrogen sulfide and the unsaturated triglycerides occurs in the presence of a solvent. 
     
     
       55. The process of  claim 50 , wherein the step of reacting the hydrogen sulfide and the unsaturated triglycerides occurs in the substantial absence of a solvent. 
     
     
       56. The process of  claim 50 , wherein a molar ratio of the hydrogen sulfide to unsaturated triglyceride carbon-carbon double bonds is greater than 2. 
     
     
       57. The process of  claim 50 , wherein the step of reacting the hydrogen sulfide and the unsaturated triglycerides is catalyzed by a heterogeneous catalyst or a homogeneous catalyst. 
     
     
       58. The process of  claim 50 , wherein the step of reacting the hydrogen sulfide and the unsaturated triglycerides is initiated by a free-radical initiator or by UV radiation. 
     
     
       59. The process of  claim 50 , wherein the thiol ester molecules have an average of greater than 5 weight percent thiol sulfur. 
     
     
       60. The process of  claim 50 , wherein the step of reacting the hydrogen sulfide and the unsaturated triglycerides occurs at a temperature of greater than −20° C. 
     
     
       61. The process of  claim 50 , wherein greater than 40 percent of the thiol ester molecule total side chains contain sulfur. 
     
     
       62. The process of  claim 50 , wherein the process is a continuous process, and the step of reacting the hydrogen sulfide and the unsaturated triglycerides is performed in an absence of a solvent, at a temperature of greater than −20° C., and is initiated by UV radiation. 
     
     
       63. A process for producing a thiol ester composition comprising the steps of:
 a) contacting hydrogen sulfide and an unsaturated ester composition comprising unsaturated natural source oils, 
 the unsaturated natural source oils having
 an average of at least 1.5 ester groups per unsaturated natural source oil molecule, and 
 an average of at least 1.5 carbon-carbon double bonds per unsaturated natural source oil molecule; and 
 
 b) reacting the hydrogen sulfide and the unsaturated natural source oils to form a thiol ester composition comprising thiol ester molecules, 
 the thiol ester molecules having
 an average of at least 1.5 ester groups per thiol ester molecule, 
 an average of at least 1.5 thiol groups per thiol ester molecule, and 
 an average molar ratio of cyclic sulfides to thiol groups of between 0.05 and 1. 
 
 
     
     
       64. The process of  claim 63 , wherein the unsaturated natural source oils are soybean oil, corn oil, castor bean oil, or canola oil. 
     
     
       65. The process of  claim 63 , wherein the unsaturated natural source oils comprise soybean oil. 
     
     
       66. The process of  claim 63 , wherein the unsaturated natural source oils are soybean oil, corn oil, castor bean oil, or canola oil, and
 the thiol ester molecules have
 an average of from 2.5 to 5 ester groups per thiol ester molecule, 
 an average of 2 to 4 thiol groups per thiol ester molecule, and 
 an average of from 6 to 15 weight percent thiol sulfur per thiol ester molecule. 
 
 
     
     
       67. The process of  claim 63 , wherein the step of reacting the hydrogen sulfide and the unsaturated natural source oils occurs in the presence of a solvent. 
     
     
       68. The process of  claim 63 , wherein the step of reacting the hydrogen sulfide and the unsaturated natural source oils occurs in the substantial absence of a solvent. 
     
     
       69. The process of  claim 63 , wherein a molar ratio of the hydrogen sulfide to unsaturated natural source oil carbon-carbon double bonds is greater than 2. 
     
     
       70. The process of  claim 63 , wherein the step of reacting the hydrogen sulfide and the unsaturated natural source oils is catalyzed by a heterogeneous catalyst or a homogeneous catalyst. 
     
     
       71. The process of  claim 63 , wherein the step of reacting the hydrogen sulfide and the unsaturated natural source oils is initiated by a free-radical initiator or by UV radiation. 
     
     
       72. The process of  claim 63 , wherein the thiol ester molecules have an average of greater than 5 weight percent thiol sulfur. 
     
     
       73. The process of  claim 63 , wherein the step of reacting the hydrogen sulfide and the unsaturated natural source oils occurs at a temperature of greater than −20° C. 
     
     
       74. The process of  claim 63 , wherein greater than 40 percent of the thiol ester molecule total side chains contain sulfur. 
     
     
       75. The process of  claim 63 , wherein the process is a continuous process, and the step of reacting the hydrogen sulfide and the unsaturated natural source oils is performed in an absence of a solvent, at a temperature of greater than −20° C., and is initiated by UV radiation.